CN115624972A - Preparation method and application of catalyst for preparing amine by amide hydrogenation - Google Patents
Preparation method and application of catalyst for preparing amine by amide hydrogenation Download PDFInfo
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- CN115624972A CN115624972A CN202211359480.1A CN202211359480A CN115624972A CN 115624972 A CN115624972 A CN 115624972A CN 202211359480 A CN202211359480 A CN 202211359480A CN 115624972 A CN115624972 A CN 115624972A
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- amide
- hydrogenation
- amine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 150000001408 amides Chemical class 0.000 title claims abstract description 78
- 150000001412 amines Chemical class 0.000 title claims abstract description 69
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 54
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 14
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- QUNLSZQCNCTKKJ-UHFFFAOYSA-K ruthenium(3+);trinitrite Chemical compound [Ru+3].[O-]N=O.[O-]N=O.[O-]N=O QUNLSZQCNCTKKJ-UHFFFAOYSA-K 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000002153 concerted effect Effects 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 6
- -1 amine compound Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a catalyst for preparing amine by amide hydrogenation, which comprises the following steps: s1, weighing a ruthenium precursor, adding water, and stirring for dissolving to obtain a ruthenium solution; s2, dropwise adding the ruthenium solution into metatitanic acid, and stirring for 0.5-1 h to obtain a mixed solution; s3, drying the mixed solution at 50-150 ℃, heating to 300-400 ℃ for 0.5-6h, roasting for 0.5-6h, and then naturally cooling to obtain Ru/TiO 2 A catalyst. The preparation method of the catalyst for preparing amine by amide hydrogenation is realized by adding Ru/TiO 2 Catalyst with strong acid and noble metal ruthenium introduced simultaneouslyThe active substance, the strong acid is sulfonic acid, phosphoric acid or halogenated acid, carbonyl in the amide has aldol condensation reaction under the acidic catalysis condition, the generated acetal is transferred to the surface of the noble metal ruthenium from the surface of the acid catalyst, the acetal is subjected to hydrodeoxygenation to obtain amine, and the strong acid active substance and the noble metal ruthenium active substance have concerted catalysis, thereby being beneficial to the industrialization of amide hydrogenation.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a catalyst for preparing amine by amide hydrogenation.
Background
The organic amine compound is an important chemical raw material and is widely applied to the synthesis of fine chemical engineering and medical intermediates; traditionally, such amine compounds are prepared by reducing amides with lithium aluminum hydride, borane and silane to obtain amines, but lithium aluminum hydride is a very active metal hydride, and is violently combusted when contacting air and water, and simultaneously releases hydrogen, which may explode. Silane is very active in chemical property, is very easy to spontaneously combust and explode, and is absorbed into human bodies to cause silicon deposition and cannot be degraded. Borane is also very reactive in chemical nature, highly pyrophoric and explosive, and is also a highly toxic substance that can cause poisoning of the lung, liver, kidneys and bible system upon inhalation. And the excess of lithium aluminum hydride, silane and borane introduces a large amount of hazardous waste, and separation after the reaction requires a large amount of energy consumption.
The preparation of amine by amide catalytic hydrogenation is the most green and environment-friendly technical scheme at present, and the amine is directly synthesized by hydrogenation by using a ruthenium homogeneous catalyst at present, but the use amount of ruthenium is large, the cost is high, noble metal and ligand of the homogeneous catalyst need to be separated, the separation difficulty is increased, and the application of the homogeneous catalyst in amide hydrogenation is further inhibited.
Disclosure of Invention
The invention aims to overcome and supplement the defects in the prior art, and provides a preparation method of a catalyst for preparing amine by amide hydrogenation. The technical scheme adopted by the invention is as follows:
a method for preparing a catalyst for preparing amine by amide hydrogenation, wherein: the method comprises the following steps:
s1, weighing 2.703g of ruthenium precursor, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution into 20-50g of metatitanic acid, and stirring for 0.5-1 h to obtain a mixed solution;
s3, drying the mixed solution at 50-150 ℃, heating to 300-400 ℃ for 0.5-6h, roasting for 0.5-6h, and then naturally cooling to obtain Ru/TiO 2 A catalyst.
Preferably, the preparation method of the catalyst for preparing amine by amide hydrogenation comprises the following steps: step S1, the ruthenium precursor is selected from one or more of ruthenium trichloride, ruthenium amine chloride, ruthenium nitrite and ruthenium amine nitrite.
Preferably, the preparation method of the catalyst for preparing amine by amide hydrogenation comprises the following steps: in the step S1, the metatitanic acid contains an acidic group selected from one or more of a sulfonic acid group, a phosphoric acid group, and a chloride ion.
The application of the catalyst prepared by the preparation method of the catalyst for preparing amine by amide hydrogenation in the preparation of amine by amide hydrogenation is disclosed, wherein:
adding 100g of amide into 10-200g of alcohol solvent, and adding 0.1-10gRu/TiO 2 The catalyst and 0.1-40g of organic amine additive react for 8-12 h under the hydrogen pressure of 0.1-8MPa, and the reaction temperature is controlled to be 80-300 ℃.
Preferably, the catalyst is used for preparing amine by amide hydrogenation, wherein:
the structural formula of the amide is as follows:
wherein R is a C1-C20 hydrocarbon and R1 and R2 are C1-C10 hydrocarbons.
Preferably, the catalyst is used for preparing amine by amide hydrogenation, wherein: the alcohol solvent is selected from one or more of methanol, ethanol, isopropanol, ethylene glycol and glycerol.
Preferably, the catalyst is used for preparing amine by amide hydrogenation, wherein: the organic amine auxiliary agent is selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, triethylamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide.
Preferably, the catalyst is used for preparing amine by amide hydrogenation, wherein: the hydrogen pressure is 2-3MPa.
Preferably, the catalyst is used for preparing amine by amide hydrogenation, wherein: the reaction temperature is 100-200 ℃.
The invention has the advantages that:
the invention relates to a preparation method and application of a catalyst for preparing amine by amide hydrogenation, which is prepared by Ru/TiO 2 The strong acid and the noble metal ruthenium catalyst active substance are simultaneously introduced into the catalyst, the strong acid is sulfonic acid, phosphoric acid or halogenated acid, carbonyl in amide generates aldol condensation reaction under the acid condition, generated acetal is transferred to the surface of the noble metal ruthenium from the surface of the acid catalyst, the acetal is hydrogenated and deoxidized to obtain amine, the strong acid active substance and the noble metal ruthenium active substance play a role in concerted catalysis, and the reaction temperature and the reaction pressure are further reduced due to concerted catalysis, so that the catalyst is more favorable for the concerted catalysisIndustrialization of amide hydrogenation.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution into 27.55g of metatitanic acid (containing sulfonic acid groups), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5 percent of Ru/TiO 2 A catalyst.
Ru/TiO obtained above 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 and R2 being methyl, was added to 30g of ethanol solvent, and 5g of Ru/TiO were added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 2
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing phosphoric acid groups), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst.
Ru/TiO obtained as described above 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 and R2 being methyl, was added to 30g of ethanol solvent, and 50g of Ru/TiO were added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 3
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution into 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst.
Ru/TiO obtained as described above 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of an amide, R being ethyl, R1 and R2 being methyl, was added to 30g of an ethanol solvent, and 5g of Ru/TiO was added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 4
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst;
mixing Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of an amide, R being ethyl, R1 and R2 being ethyl, was added to 30g of an ethanol solvent, and 5g of Ru/TiO was added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 5
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, mixingDrying the resultant solution at 100 deg.C, heating to 400 deg.C for 1 hr, calcining for 2 hr, and naturally cooling to obtain 5% Ru/TiO 2 A catalyst.
Mixing Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, are added to 30g of ethanol solvent, and 5g of Ru/TiO are added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 6
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution into 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5 percent of Ru/TiO 2 A catalyst.
Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, are added to 30g of ethanol solvent, and 5g of Ru/TiO are added 2 The catalyst and 5g of triethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 7
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst.
Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: adding 100g of amide, R of which is ethyl, R1 is phenyl, R2 is ethyl, to 30g of ethanol solvent, and adding5g of Ru/TiO 2 The catalyst and 5g of trimethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 8
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst.
Mixing Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, are added to 30g of ethanol solvent, and 5g of Ru/TiO are added 2 The catalyst and 5g of trimethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 9
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium nitrite, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5 percent of Ru/TiO 2 A catalyst.
Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, are added to 30g of ethanol solvent, and 5g of Ru/TiO are added 2 The catalyst and 5g of trimethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 10
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium nitrite, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5 percent of Ru/TiO 2 A catalyst.
Mixing Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, are added to 30g of ethanol solvent, and 5g of Ru/TiO are added 2 The catalyst and 5g of trimethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 11
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1h, roasting for 2h, and then naturally cooling to obtain 5% of Ru/TiO 2 A catalyst.
Mixing Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, was added to 30g of isopropanol solvent, and 5g of Ru/TiO were added 2 The catalyst and 5g of trimethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
Example 12
A preparation method of a catalyst for preparing amine by amide hydrogenation comprises the following steps:
s1, weighing 2.703g of ruthenium trichloride, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution to 27.55g of metatitanic acid (containing chlorine), and stirring for 1h to obtain a mixed solution;
s3, drying the mixed solution at 100 ℃, heating to 400 ℃ for 1 hour, roasting for 2 hours, then naturally cooling,to yield 5% Ru/TiO 2 A catalyst.
Ru/TiO 2 The catalyst is subjected to amide hydrogenation to prepare amine: 100g of amide, R being ethyl, R1 being phenyl, R2 being ethyl, was added to 30g of isopropanol solvent, and 5g of Ru/TiO were added 2 The catalyst and 5g of diethylamine are reacted for 12 hours under the hydrogen pressure of 2.5MPa, and the reaction temperature is controlled to be 150 ℃.
The yields of amines produced by the hydrogenation of amides of examples 1-12 are shown below in Table 1.
TABLE 1 yield of amine from amide hydrogenation
As can be seen from Table 1, the hydrogenation of amide under the action of ruthenium catalyst and organic amine promoter to prepare amine has mild reaction conditions and higher amine yield compared with the prior art of amide hydrogenation.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a catalyst for preparing amine by amide hydrogenation is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing 2.703g of ruthenium precursor, adding 54g of water, and stirring for dissolving to obtain a ruthenium solution;
s2, dropwise adding the ruthenium solution into 20-50g of metatitanic acid, and stirring for 0.5-1 h to obtain a mixed solution;
s3, drying the mixed solution at 50-150 ℃, and heating for 0.5-6hRoasting for 0.5-6h at 300-400 ℃, and then naturally cooling to obtain Ru/TiO 2 A catalyst.
2. The method of claim 1 for preparing a catalyst for the hydrogenation of amides to amines, comprising: the ruthenium precursor in the step S1 is selected from one or more of ruthenium trichloride, ruthenium amine chloride, ruthenium nitrite and ruthenium amine nitrite.
3. The method for preparing a catalyst for preparing amine by amide hydrogenation according to claim 1, wherein: in the step S1, the metatitanic acid contains an acidic group selected from one or more of a sulfonic acid group, a phosphoric acid group, and a chloride ion.
4. Use of a catalyst prepared by the process for preparing an amine by hydrogenating an amide according to any one of claims 1 to 3 in the preparation of an amine by hydrogenating an amide, wherein:
adding 100g of amide into 10-200g of alcohol solvent, and adding 0.1-10gRu/TiO 2 The catalyst and 0.1 to 40g of organic amine auxiliary agent react for 8 to 12 hours under the hydrogen pressure of 0.1 to 8MPa, and the reaction temperature is controlled to be 80 to 300 ℃.
5. Use of the catalyst of claim 4 for the preparation of amines by hydrogenation of amides, characterized in that: the structural formula of the amide is as follows:
wherein R is a C1-C20 hydrocarbon, and R1 and R2 are C1-C10 hydrocarbons.
6. Use of the catalyst of claim 4 for the preparation of amines by hydrogenation of amides, characterized in that: the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, ethylene glycol and glycerol.
7. Use of the catalyst of claim 4 for the hydrogenation of amides to amines, wherein: the organic amine auxiliary agent is selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, triethylamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide.
8. Use of the catalyst of claim 4 for the hydrogenation of amides to amines, wherein: the hydrogen pressure is 2-3MPa.
9. Use of the catalyst of claim 4 for the hydrogenation of amides to amines, wherein: the reaction temperature is 100-200 ℃.
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